Light-sensitive photographic element



Patented Sept. 23, 1952 ELEMENT Ren Adriaan Stevens, Antwerp, Laurent Aloys Van Der Auwera, Mortseli-Antwerp",.andDsir- Maria Aloysius Van" Goethem, KontiehpBel-g' gium, assignors to Gevaert Photo-Producten of Belgium N. V., Mortsel-Antwerp, Belgium, a company No Drawing. ApplicatiomApril '15, 1947,- Serial 1 I i No. 741,684. In Germany- April- 22 194 2- Section LPublic Law 690, August s, 1946 Patent expires April 22, 1962 3Claims. 1 This invention relates to colored photographic layers, especially filter and anti-halation layers having no binding agent, and to aprocess for manufacturing the same.

Anti-halation layers have to meet the following requirements: their absorptive power should be adapted to the optical sensitivity of the silver halide emulsions; they should lose color quickly,

completely and irreversibly in weak alkaline developing baths; and their decompositionproducts should exert noinfluence on the development or on the photographic properties of the emulsion. The layers should also withstand mechanical influences which remove the dyestufi itself or which could damage the thin layer.

The known anti-halation. layers. meet only one of the above listed requirements, that is to say, it is known to use irreversibly discoloring antihalationlayers characterised by the presence of condensation products of substituted aromatic aldehydes with quaternary heterocyclic. bases containing a reactive methyl group. Condensation products of equimolar quantities of aromatic or cyclic aldehydes with cyclic combinations containing a reactive methylene group, or condensation products of dehydracetic acid with aromatic aldehydes and ketones, respectively, have also been used for the same purpose.

In order to obtain the desired resistanceof the layers, the use of. synthetic resins as binding agents for the dyestuff, or the varnishing of the layer with natural or synthetic resins containing at least one self-forming hydroxyl or carboxyl group and being soluble in alkaline baths, has been proposed.

It is among the objects of our invention to generally improve colored photographic layers, particularly to provide filter and anti-halation layers having several of the above mentioned properties simultaneously.

A further object of our present invention is to provide a photographic light-sensitive single or multi-layer silver halide material containing at least one of the said colored photographic layers.

To the accomplishment of the foregoing and other more detailed objects which will hereinafter appear, our invention consists in the prodnot and the method of producing same, as hereinafter are more particularly described in the methine dyestuffs of the type that is obtainable as, for, instance," by condensationof substituted or unsubstituted aliphatic, aromatic or heterocyclic' aldehydes with suitablesubstituted anilcines' oramines, preferably in equimolar' quanti By using these salts, the color intensity of the dyestuffs is considerably increased. Additionally, the unexpected fact has been noticed that these dye salts produce intense dyestuiis whichd'iscolor irreversibly in weak alkaline developers and also possess the property of forming an intensively'colored varnish layer .from' an aqueous or alcoholic solution without the use of a binding agenti For the manufacturing of the azomethirie dyestufis the following amines may be used:-

ortho amidobenzoic' acid,

. amidosalicyclicacid;

.para-amidobenzoic;acid, ,benzidin,

para-anisidin, para-amidodiphenylam-ine, ortho-anisidin, para-toluylediamine, l m. dibromoanthranilic acid, aminophenyltliiocarbamide.

Suitable aldehydes are, ea g.,. para-dimethyl- Example 1 1 mol anthranilic acid and 1 mol para-dimethylaminobenzaldehyde are heated in a diluted alcoholic solution. A colored combination separates immediately and is crystallised from alcohol (iJOOBK 3 .ErampZe 2 1 mol anisic aldehyde is condensed as in Example 1 with 1 mol amidodiphenylamine to an azomethine dyestufi of the following probable structure This azomethlne dye base is condensed in equimolar proportions with salicyclic acid in alcohol.

Example 3 COOH All of the above dyestuffs are suitable for all photographic purposes where a layer discolorable in a weak alkaline medium is required, as e. g. for filter layers, anti-halation layers, back layers, and also for direct addition to the silver halide emulsion.

It is behaved that the general method and the specific examples of our invention, as well as the advantages thereof, will be apparent from the foregoing detailed description. It will also be apparent that while we have shown and described preferred examples of our invention, changes may be made without departing from the spirit of the invention, as sought to be defined in the following claims.

We claim:

1. Photographic material containing at least one light-sensitive silver'halide emulsion layer and a colored non-sensitive layer including the reaction product of a basic azomethine dyestuif, obtained by condensing in equimolar proportions an aldehyde selected from the group consisting of p-dimethylaminobenzaldehyde and p-dimethylaminocinnamic aldehyde, and anthranilic acid, with methylene disalicylic acid, said reaction product; corresponding to the following formula:

wherein A represents the atoms necessary to complete with H benzoic acid, B represents the atoms necessary to complete with OHC- an aldehyde selected from said group of aldehydes, R represents the atoms necessary to complete with H methylene disalicylic acid, the radical of the latter acid being linked to the N-atom so that 4 the salt-formingOI-I remains intact, and n represents a positive integer of from 1 to 2.

2. Photographic material containing at least one light-sensitive silver halide emulsion layer and a colored non-sensitive layer including the dyestuff of the formula:

coon

000 (JH oooH "no -on 3. Photographic material containing at least one' light-sensitive silver halide emulsion layer and a colored non-sensitive layer including the dyestuff of the formula:

CH: H

000- CH COOH HO OH RENE ADRIAAN STEVENS. LAURENT ALOYS VAN DER AUWE'RA. DESIRE MARIA ALOYSIUS VAN GOETHEM.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,879,537 Schneider Sept. 27, 1932 2,276,158 Chenicek Mar. 19, 1942 2,282,890 Schneider et al. May 12, 1942 2,336,215 Bean Dec. 7, 1943 2,388,903 Cantrell et al Nov. 13, 1945 2,396,580 Kulz Mar. 12, 1946 FOREIGN PATENTS Number Country Date 539,07 0 Great Britain Aug. 27, 1941 OTHER REFERENCES Werner, Sci. Proc. Royal Dublin Soc., vol 23, pp. 214-221 (1944).

Betti et al., Beilstein (Handbuch, 4th ed.) vol. 12, page 198 (1929).

Lynch et al., J. Am. Chem. Soc., vol. 55, pages 2515-2520 (1933). 

1. PHOTOGRAPHIC MATERIAL CONTAINING AT LEAST ONE LIGHT-SENSITIVE SILVER HALIDE EMULSION LAYER AND A COLORED NON-SENSITIVE LAYER INCLUDING THE REACTION PRODUCT OF A BASIC AZOMETHINE DUESTUFF, OBTAINED BY CONDENSING IN EQUIMOLAR PROPORTIONS AN ALDEHYDE SELECTED FROM THE GROUP CONSISTING OF P-DIMETHLAMINOBENZALDEHYDE AND P-DIMETHYLAMINOCINNAMIC ALDEHYDE, AND ANTHRANILIC ACID, WITH METHYLENE DISALICYLIC ACID, SAID REACTION PRODUCT CORRESPONDING TO THE FOLLOWING FORMULA 